Process for combating micro-organisms, and novel phthalocyanine compounds

Abstract

A process for combating micro-organisms in or on organic or inorganic substrates and for protecting the said substrates against attack by micro-organisms, which comprises treating the substrates with a water-soluble phthalocyanine derivative, in the presence of oxygen and water and while irradiating with light in the infra-red and/or visible range, antimicrobical agents containing water-soluble phthalocyanine compounds as well as new phthalocyanine compounds are described.

What is claimed is: 
     
       1. A process for combatting microorganisms in or on organic or inorganic substrates and for protecting said substrates against attack by microorganisms, which comprises treating the substrates with an effective amount of a watersoluble phthalocyanine derivative, which is a metal-free phthalocyanine derivative or a metal complex thereof which contains, as the metal atom, aluminum, zinc, iron-II, calcium, magnesium, sodium or potassium, said derivative contains, as groups conferring solubility in water, sulpho or carboxyl groups and their salts, or groups of the formulae ##STR40## in which formula X 1  is oxygen or a --NH-- or --N-alkyl radical and R 1  and R 2  independently of one another are hydrogen, a sulpho groups and salts thereof, a carboxyl group and salts thereof or a hydroxyl group, at least one of the radicals R 1  and R 2  being a sulpho or carboxyl group or a salt thereof, Y 1  is oxygen, sulphur or a --NH-- or --N-alkyl radical, R 3  and R 4  independently of one another are hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenoalkyl having 1 to 6 carbon atoms, unsubstituted phenyl or phenyl substituted by halogen, alkyl or alkoxy having 1 to 4 carbon atoms, sulpho or carboxyl, or R 3  and R 4  together with the nitrogen atom to which they are bonded are a saturated 5-membered or 6-membered heterocyclic ring, which additionally can also contain a nitrogen atom or oxygen atom as a ring member, R 5  and R 6  independently of one another are substituted or unsubstituted alkyl or aralkyl radical, R 7  is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or hydrogen, M is an alkali metal ion or ammonium ion, Z.sup.θ is an anion, for example a chlorine, bromine, alkyl-sulphate or aralkyl-sulphate ion, n is an integer from 2 to 12 and m' is 0 or 1, the number of groups conferring solubility in water, which can be of the same type or different, being at least sufficiently large to ensure that an adequate solubility in water is obtained, said phthalocyanine derivative also optionally containing other substitutes in addition to the groups conferring solubility in water, the amount of said phthalocyanine derivative employed being insufficient to cause substantial discoloration of the substrate, in the presence of oxygen and water and with concurrent irradiation with light in the infra-red and/or visible range of sufficient intensity to effect disinfection. 
     
     
       2. A process according to claim 1, which comprises carrying out the process in the presence of an inorganic salt. 
     
     
       3. A process according to claim 1 for combating bacteria. 
     
     
       4. A process according to claim 1 for disinfecting swimming pools and effluents from sewage treatment plants, which comprises adding 0.001 to 100 ppm of one or more of the phthalocyanine derivatives. 
     
     
       5. A process according to claim 1 which comprises using, as the water-soluble phthalocyanine derivative, a derivative of the formula   (Me).sub.m (PC--(R).sub.v     in which PC is the phthalocyanine ring system, v has any desired value between 1 and 4, Me is Zn, Fe(II), Ca, Mg, Na, K or AlX, in which X is an anion, m is 0 or 1 and R is a group of the formula ##STR41## in which Y is hydrogen or an alkali metal, ammonium or amine ion, R 7  ' is hydrogen or alkyl having 1 to 4 carbon atoms, n' is an integer from 2 to 6, R 1  and R 2  independently of one another are hydrogen, a sulpho group and salts thereof, a carboxyl group and salts thereof or a hydroxyl group and at least one of the radicals R 1  and R 2  is a sulpho or carboxyl group or a salt thereof, and R 3  and R 4  independently of one another are hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenoalkyl having, in each case, 1 to 6 carbon atoms, or phenyl, or R 3  and R 4  together with the nitrogen atom to which they are bonded are a saturated 5-membered or 6-membered heterocyclic ring, which additionally can also contain a nitrogen atom or oxygen atom as a ring member, and, when several radicals R are present in the molecule, these radicals can be identical or different, and all the radicals R are bonded to the phenyl nuclei of the phthalocyanine ring system.   
     
     
       6. A process according to claim 5, which comprises using, as the water-soluble phthalocyanine derivative, a derivative of the formula ##STR42## in which PC, Me and m are as defined in claim 5, n' is an integer between 2 and 6, R 3  ' and R 4  ' independently of one another are hydrogen, phenyl, sulphophenyl, carboxyphenyl or alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenoalkyl having, in each case, 1 to 6 carbon atoms, or together with the nitrogen atom are the morpholine ring, and v is a number between 1 and 4, and, if v>1, the radicals ##STR43## present in the molecule can be identical or different. 
     
     
       7. A process according to claim 5, which comprises using, as the water-soluble phthalocyanine derivative, a derivative of the formula ##STR44## in which PC, Me and m are as defined in claim 5, Y' is hydrogen or an alkali metal or ammonium ion, n' is an integer between 2 and 6, R 3  ' and R 4  ' independently of one another are hydrogen, phenyl, sulphophenyl, carboxyphenyl or alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenoalkyl having, in each case, 1 to 6 carbon atoms, or together with the nitrogen atom are the morpholine ring, m' is 0 or 1 and w and w 1  independently of one another are any desired number between 0.5 and 3, and w+w 1  is at least 1, but at most 4. 
     
     
       8. A process according to claim 1, which comprises carrying out the treatment of the particular substrate in an aqueous bath which contains the water-soluble phthalocyanine active compound in a concentration of 0.1 to 50 mg/l. 
     
     
       9. A process according to claim 8, which comprises carrying out the irradiation with a filament lamp or infra-red lamp, either in the treatment bath or outside the treatment bath. 
     
     
       10. A process according to claim 8, which comprises irradiating the substrate in sunlight. 
     
     
       11. A process according to claim 1 for combating microorganisms on textile materials and for protecting the said materials against attack by micro-organisms, which comprises treating these materials, in the presence of oxygen and while irradiating with visible or infra-red light, with an aqueous solution which contains said phthalocyanine derivative. 
     
     
       12. A process according to claim 11 for disinfecting goods to be washed, which comprises washing the goods to be washed, while irradiating with infra-red or visible light, in a wash liquor which contains, in addition to conventional constituents of washing agents, 0.001 to 100 ppm of one or more of the phthalocyanine derivatives. 
     
     
       13. A process according to claim 11 for disinfecting or finishing textiles, which comprises treating the latter in a liquor which contains 0.01 to 50 ppm of said phthalocyanine derivative, the bath being irradiated direct with an artificial light source or the textiles, in the damp state, subsequently being irradiated with an artificial light source or exposed to sunlight. 
     
     
       14. A process according to claim 1, which comprises using a phthalocyanine derivative, or a metal complex thereof, which is substituted on the phenyl nuclei by said acid or basic groups. 
     
     
       15. A process according to claim 14, which comprises using, as a phthalocyanine derivative having basic substituents, or a metal complex thereof, a derivative or complex in which the phenyl nuclei contain sulphanoyl or alkoxysulphonyl groups having basic substituents and/or quaternary ammonium groups, the total number of substituents being between 2 and 4. 
     
     
       16. A process according to claim 15, which comprises using a phthalocyanine derivative, or a metal complex thereof, which carries, on the phenyl nuclei, substituents of the formula ##STR45## in which n is a number between 2 and 12 and R 3  and R 4  independently of one another are hydrogen, alkyl, hydroxyalkyl, cyanoalkyl or halogenoalkyl having, in each case, 1 to 12 carbon atoms, or R 3  and R 4  together with the nitrogen atom to which they are bonded form a saturated 5-membered or 6-membered heterocyclic ring, which if desired can additionally also contain a nitrogen atom or oxygen atom as a ring member. 
     
     
       17. A process according to claim 14, which comprises using a metal-free phthalocyanine derivative. 
     
     
       18. A process according to claim 17, which comprises using a phthalocyanine derivative of the formulae defined in claims 8, 11 or 12, in which m is 0. 
     
     
       19. A process according to claim 14, which comprises using a metal complex of a phthalocyanine derivative. 
     
     
       20. A process according to claim 19, which comprises using an aluminium or zinc complex of a phthalocyanine derivative. 
     
     
       21. A process according to claim 14, which comprises using, as a phthalocyanine derivative having acid substituents, or a metal complex thereof, a derivative or complex which is substituted by sulpho groups and/or carboxyl groups or radicals containing such groups. 
     
     
       22. A process according to claim 21, which comprises employing a sulphonated phthalocyanine or a metal complex thereof. 
     
     
       23. A process according to claim 22, which comprises using the aluminium or zinc complex of a sulphonated phthalocyanine having a degree of sulphonation of 1 to 4 and preferably 1.5 to 4. 
     
     
       24. A process according to claim 22, which comprises using a sulphonated phthalocyanine derivative of the formula   (Me).sub.m (PC--(SO.sub.3 Y').sub.v     in which PC is the phthalocyanine ring system, Y' is hydrogen or an alkali metal or ammonium ion, v is any desired number between 1 and 4 (the degree of sulphonation), m is 0 or 1 and Me is Zn, Fe(II), Ca, Mg, Na, K or AlX, in which X is an anion, especially a halide, sulphate, hydroxyl or acetate ion.   
     
     
       25. A process according to claim 24, which comprises using a phthalocyanine derivative in which m is 1 and Me is Zn or AlX. 
     
     
       26. A process according to claim 25, which comprises using a phthalocyanine derivative in which m is 1 and Me is AlX.